Steel plate for paint use and manufacturing method thereof

ABSTRACT

A steel plate for paint use which contains C (0.12% or less), Si (1.0% or less), Mn (2.5% or less), P (0.05% or less), S (0.02% or less), and Cr (0.05% or less), Cu (0.05-3.0%), Ni (0.05-6.0%), Ti (0.025-0.15%), and Cu+Ni (0.50% or more), with P CM  being 0.23% or less, in terms of mass %. Said steel plate may contain at least one additional component selected from B (0.0005-0.0030%), Al (0.05-0.50%), Ca (0.0001-0.05%), Ce (0.0001-0.05%), La (0.0001-0.05%), Nb (0.002-0.05%), V (0.01-0.10%), Zr (0.002-0.05%), and Mo (0.05-0.5%), in terms of mass %.  
     This steel plate provides good weldability as well as good painting durability in a salt-polluted environment.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The present invention relates to a steel plate to be used forsteel structures (such as bridges and towers) which present difficultiesin routine maintenance work such as repainting and also to amanufacturing method thereof. More particularly, the present inventionrelates to a steel plate to be used with a painted film in coastland orcold district where steel structures are subjected to salt damage byairborne salt or deicing salt (as an antifreezing agent scattered on theroad) and also to a manufacturing method thereof.

[0003] 2. Description on the Related Art

[0004] There are two kinds of corrosion-resistant steels specified inthe Japanese Industrial Standards (JIS). They are corrosion-resistanthot-rolled steel for welded structures (designated as SMA, JIS G-3114)and highly corrosion-resistant rolled steel (designated as SPA, JISG-3125). These steels contain Cr, Cu, Ni, P, etc. in an adequate amount.Such corrosion-resistant steels are also disclosed in Japanese patentsmentioned later. Corrosion-resistant steels form a dense and excellentlyadhesive layer of stable rust thereon which protects them fromcorrosion. They have been widely used in inland areas.

[0005] Unfortunately, corrosion-resistant steels need a long time of 10years or more until they form a layer of stable rust. Practically, theypose a problem of initial corrosion and rust-laden water. This is trueparticularly in Japan where the climate is warm and humid. Ruststabilization is common practice to prevent corrosion-resistant steelsfrom posing landscape or environment with rust-laden water until theyform stable rust when they are used without a painted film. Thispractice, however, merely avoids rust-laden water and hinders theformation of compact rust layer when steels are used in a salt-pollutedenvironment.

[0006] Several means have been proposed to address the above-mentionedproblems involved in corrosion-resistant steels. For example, resinpainting on the surface of corrosion-resistant steel, which is intendedto promote the formation of stable rust while isolating steel surfacefrom its environment, is disclosed in Japanese Patent Publication Nos.22530/1978, 33991/1981, 39915/1983, 17833/1983, and 21273/1994, andJapanese Patent Laid-open No. 133480/1990. A surface treating solutionto promote the formation of stable rust, which contains Fe₃O₄ of scalycrystal structure, phosphoric acid, and butyral resin dissolved in asolvent, is disclosed in Japanese Patent Laid-open No. 133480/1990. Amethod of surface treatment for rust stabilization, which consists ofapplying a painting solution composed of more than one compound of P,Cu, Cr, N, Si, and Mo, Fe₂O₃+Fe₃O₄, phosphoric acid, a bisphenol epoxyresin, and auxiliaries dissolved in a solvent, is disclosed in JapanesePatent Publication No. 21273/1994. The above-mentioned means, however,neither improve the corrosion-resistant steels themselves nor promotethe formation of stable rust satisfactorily. In other words, a resinpainted film usually has minute defects at which the film effect is notproduced. Such defects cause corrosion to take place in the interfacebetween the painted film and base metal, with the result that thepainted film exfoliate before the stable rust layer is formed.Therefore, the use of corrosion-resistant steel is limited in thesalt-polluted environment.

[0007] In the meantime, an important subject in the world of bridge isto save maintenance cost for repainting as well as construction cost.The latter object is achieved by reducing the number of main girders,adopting rationalized girders, reducing the frequencies of site welding,and reducing maintenance management. This stimulates a demand for steelwith large thickness and high strength capable of welding with a largeamount of heat input which obviates preheating to prevent cold crackingat the time of welding.

OBJECT AND SUMMARY OF THE INVENTION

[0008] The present invention was completed in order to address theabove-mentioned problems. Accordingly, it is an object of the presentinvention to provide a steel plate for paint use and a manufacturingmethod thereof, said steel plate imparting good durability to thepainted film thereon when used in a salt-polluted environment and alsobeing superior in weldability.

[0009] The gist of the present invention resides in a steel plate forpaint use which contains C (0.12% or less), Si (1.0% or less), Mn (2.5%or less), P (0.05% or less), S (0.02% or less), Cr (0.05% or less), Cu(0.05-3.0%), Ni (0.05-6.0%), Ti (0.025-0.15%), Cu+Ni (0.50% or more),and Pa (0.23% or less), in terms of mass %.

[0010] The above-specified steel plate may contain at least oneadditional component selected from B (0.0005-0.0030%), Al (0.05-0.50%),Ca (0.0001-0.05%), Ce (0.0001-0.05%), La (0.0001-0.05%), Nb(0.002-0.05%), V (0.01-0.10%), Zr (0.002-0.05%), and Mo (0.05-0.5%), interms of mass %.

[0011] The above-specified steel plate, with the Ti/C ratio higher than4, is produced by hot-rolling in such a way that the heating temperature(T) is 850-1200° C. and the temperature at the end of rolling is 950° C.or lower, which is followed by air cooling or water cooling (at acooling rate 1° C./s or higher), or by direct quenching from atemperature of Ar₃˜950° C. or reheating-quenching from a temperature ofAc₃˜950° C., and tempering.

[0012] The above-specified steel plate, with the Ti/C ratio 4 or lower,is produced by hot-rolling in such a way that the heating temperature(T) is 850≦T≦(1200−50×Ti/C) ° C. and the temperature at the end ofrolling is (Ar₃+50×Ti/C+100×Ni²) ° C. or lower, which is followed by aircooling or water cooling (at a cooling rate 1° C./s or higher), or bydirect quenching from a temperature at the end of rolling orreheating-quenching from a temperature of (Ac₃+50×Ti/C+100×Ni²) ° C. orlower, and tempering. P_(CM), Ar₃, and AC₃ used above are defined asfollows.

[0013] P_(CM)=C+Si/30+Mn/20+Cu/20+Ni/60+Cr/20+Mo/15+V/10+5B

[0014] Ar₃=910−310C−80Mn−20Cu−15Cr−55Ni−80Mo+0.35(t−8) (where trepresents the plate thickness.)

[0015] Ac₃=908−223.7C+438.5P+30.49Si+37.92V−34.43Mn−23Ni+2(100C−54+6Ni)(where the term 2(100C−54+6Ni) is applicable only when it is positive.)

BRIEF DESCRIPTION OF THE DRAWINGS

[0016]FIG. 1 is a graph showing how toughness is affected by the heatingtemperature and the Ti/C ratio.

[0017]FIG. 2 is a graph showing how toughness is affected by thedifference between FRT and Ar₃ and the Ti/C ratio, in the case where theamount of Ni is 1.0%.

[0018]FIG. 3 is a graph showing how toughness is affected by thedifference between FRT and Ar₃ and the Ti/C ratio, in the case where theamount of Ni is 0.5%.

[0019]FIG. 4 is a graph showing how toughness is affected by thedifference between the quenching temperature and Ac₃ and the Ti/C ratio,in the case where the amount of Ni is 1.0%.

[0020]FIG. 5 is a graph showing how toughness is affected by thedifference between the quenching temperature and Ac₃ and the Ti/C ratio,in the case where the amount of Ni is 0.5%.

[0021]FIG. 6 is a figure showing the shape of the specimen subjected tothe accelerated test and the atmospheric exposure test.

[0022]FIG. 7 is a figure illustrating the cycle of accelerated tests.

[0023]FIG. 8 is a graph showing the relation between the corrosionresistance and the total amount of Cu+Ni.

[0024]FIG. 9 is a graph showing the relation between the corrosionresistance and the amount of Ti added.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0025] It is known that if steel has a compact stable rust layerthereon, its corrosion only proceeds at a negligibly low rate eventhough it has no special anti-corrosion treatment, because the rustlayer physically or electrochemically prevents corrosion-acceleratingfactors (such as moisture, oxygen, and chlorine ions present in theenvironment) from reaching the base metal (or steel). Thecorrosion-resistant steel effectively utilizes the action ofself-corrosion resistance by compact rust.

[0026] To be concrete, it is possible to obtain the corrosion-resistantsteel by adding such elements as Cr, Cu, Ni, and P, which promote theformation of compact rust, in very small amounts. In other words,corrosion-resistance steel produces its effect when it is used without apainted film. However, as mentioned earlier, the corrosion-resistantsteel does not fully produce its effect of promoting the formation ofstable rust when it is used in an environment severely contaminated withsalt. Several means to cope with this situation have been devised. Oneof them is to paint the steel surface with a thin resin film so as toprotect steel from salt until stable rust forms on the steel surface.However, the resin painted film is not satisfactory because of filmdefects as mentioned above.

[0027] The present inventors extensively studied the mechanism ofcorrosion in the defective part of a painted film. It was found that Cras a steel component is a corrosion-accelerating element. In otherwords, it was found that when steel corrosion starts at the defectivepart of a painted film, Cr dissolves together with iron atoms, givingrise to Cr ions which, in conjunction with Cl ions, lower the pH in thedefective part, thereby acidifying condensed water therein. Theresulting acid water causes corrosion in the interface between thepainted film and the base metal.

[0028] It is concluded from the mechanism of corrosion just mentionedabove that it is important to take into account the following threepoints for improvement in durability of resin-paintedcorrosion-resistant steel in salt-polluted areas.

[0029] (1) Reduce the amount of Cr as far as possible so as to removethe corrosion-accelerating element in the defective part in a paintedfilm.

[0030] (2) Add an element, in place of Cr, which promotes the formationof stable rust. (Since a painted steel has its base protected from saltby the painted film, it will have a long life even in a corrosiveenvironment so long as it contains an element which prevents the pH fromdecreasing in the defective part of the painted film.)

[0031] (3) Add an element which moderates the decrease of pH in thedefective part of a painted film or which rather increases pH whendissolved.

[0032] If the above-mentioned requirements are met, steel will formstable rust in the defective part of the painted film. Painting a commonorganic resin is recommended because of economy, workability, andsimplicity. Among various resins (such as polyester, epoxy, andurethane), butyral resin is the best because of its toughness,flexibility, impact strength, and good adhesion to metal.

[0033] The steel for paint use will permit reduction in the number ofmain girders and adoption of rationalized girders, which leads to costreduction in bridge construction, if it has good weldability, goodlow-temperature toughness, sufficient thickness, and high strength. Forthe steel plate to have good weldability, it is necessary to control theC content and the weld cracking parameter of material P_(CM). For thesteel plate to have good toughness, it is necessary to control theprecipitation of TiC or to specify the heating, rolling, andheat-treating conditions according to the Ti/C ratio. For the steelplate to have sufficient thickness and high strength, it is necessary toadd B, Nb, V, Zr, and Mo. For the steel plate to have good toughness atthe part affected by welding heat and to be capable of welding with alarge amount of heat, it is necessary to specify the upper limit of thecontent of C and Ti and to effectively utilize B.

[0034] The present invention is based on the above-mentioned ideas.Mention is made below of the effect of each composition and the reasonwhy the amount of each composition is limited.

[0035] Regarding Cu, Ni, and Ti as essential elements for thecorrosion-resistant steel.

[0036] Cu is an element which is electrochemically nobler than iron. Itforms compact rust and grows stable rust. It produces its effect when itis contained in an amount of 0,05% or more. Its effect levels off whenits content exceeds 3.0%. With an excess amount, it makes the steelbrittle at the time of hot rolling. Therefore, the adequate content ofpu should be 0.05-3.0%.

[0037] Ni is an element which, like Cu, improves corrosion resistance.It produces its effect when it is contained in an amount of 0.05% ormore. In addition, Ni prevents hot brittleness which may occur if Cu iscontained. Its effect levels off when its content exceeds 6.0%.Therefore, the adequate content of Ni should be 0.05-6.0%.

[0038] In addition, the present invention requires that the total amountof Cu+Ni be 0.50% or more. FIG. 8 shows the relation between the totalamount of Cu+Ni and the corrosion resistance, which was found by thepresent inventors' experiment with the sample according to claim 1. Thetest method is shown in FIG. 7. The test result was rated in terms ofthe width of blistering at the defective part of painted film. In FIG.8, the corrosion resistance index is indicated by 1−a (where a is theaverage width (mm) of blistering). The larger the index, the better thecorrosion resistance. It is apparent from FIG. 8 that the corrosionresistance increases according as the total amount of Cu+Ni increases.Good effects are produced when the total amount of Cu+Ni is 0.50% ormore.

[0039] Ti is an essential element to supersede Cr which was selectedunder the idea mentioned in (2) above. Like Cr, Cu, and Ni, this elementforms compact rust and grows stable rust. It also provides outstandingcorrosion resistance and produces the effect of purifying steel. Theseeffects are remarkable when the content is 0.025% or more. With itscontent exceeding 0.15%, Ti does not produce any additional effect butrather aggravates the toughness of the part affected by welding heat.Therefore, the adequate content of Ti should be 0.025-0.15%.

[0040]FIG. 9 shows the relation between the content of Ti and thecorrosion resistance, which was found by the present inventors'experiment with the sample according to claim 1. The test method and therating of the test result are the same as mentioned above. It isapparent from FIG. 9 that the corrosion resistance increases accordingas the content of Ti increases. Good effects are produced when thecontent of Ti is 0.05% or more.

[0041] Mention is made below of the effect of P, Cr, C, Si, and Mn. Pand Cr are necessary for conventional steels to be used without coating.Since they greatly aggravate weldability, their content is limited to0.05% in the steel plate of the present invention which is used mainlyfor bridges and other structures that need site welding frequently. Thecontent of Cr should not exceed 0.05%, because Cr decreases pH andacidifies condensed water in the defective part of painted film, therebycausing corrosion in the interface between the painted film and the basemetal.

[0042] C is an essential element for the steel plate to have a desiredstrength. With an increasing content of C, the steel plate becomes poorin weldability and corrosion resistance. Therefore, the content of Cshould be 0.12% or less. Incidentally, for the steel plate to havesatisfactory weldability and corrosion resistance, the content of Cshould be 0.10% or less. For good weldability, P_(CM) should be 0.23% orless according to the present invention.

[0043] Si promotes solid-solution hardening, accelerates the formationof stable rust, and improves corrosion resistance. However, Si in anexcess amount aggravates weldability. Therefore, the adequate content ofSi should be 1.0% or less.

[0044] Mn provides strength, like C. A large amount of Mn in steel hasan adverse effect on workability, toughness, and corrosion resistance(due to MnS formed from it). Therefore, the adequate content of Mnshould be 2.5% or less.

[0045] S combines with Mn or Fe to form MnS or FeS, respectively. Thesecompounds provides a starting point for corrosion. Therefore, theadequate content of S should be 0.02% or less.

[0046] Al, as well as Ti, is an element to supersede Cr which wasselected under the idea mentioned in (2) above. Like Cr, Cu, and Ni,this element forms compact rust and grows stable rust. It produces itseffect when its content is 0.05% or more. It produces an enhanced effectwhen used in combination with Ti. With an amount exceeding 0.50%, itproduces no additional effect but rather aggravates the toughness of thebase metal. Therefore, the adequate content of Al should be 0.05-0.50%.

[0047] Ca, Ce, and La are elements to moderate pH decrease in thedefective part of painted film, which were selected under the ideamentioned above in (3). These elements slightly dissolve as thecorrosion of iron proceeds under the painted film. They are alkaline andhence they moderate pH decrease, thereby preventing corrosion in thedefective part in painted film. They produce their effect when they arepresent in an amount of 0.0001% or more. Their effect levels off eventhough their amount is increased. Therefore, their respective contentshould be 0.0001-0.05%.

[0048] B is an element which improves the hardenability and strength ofsteel and forms fine ferrite in the part affected by welding heat,thereby compensating for embrittlement due to TiC precipitation, Anamount of 0.0005% or more is necessary for B to produce its effect. Anexcess amount more than 0.0030% aggravates weldability rather thanenhancing the effect. Therefore, the content of B should be0.0005-0.0030%.

[0049] Mention is made below of Mo, Nb, Zr, and V. These elements areadded to thick steel plates (50 mm and above) and high-strength steel(590 N/mm² and above), but they produce very little effect on corrosionresistance.

[0050] Mo, as well as B, is an element which effectively increases thestrength of steel. An amount of 0.05% or more is necessary for Mo toproduce its effect. An excess amount more than 0.5% aggravatesweldability rather than enhancing the effect. Therefore, the content ofMo should be 0.05-0.5%.

[0051] Nb and Zr are elements which form their carbo-nitrides toincrease strength. They produce this effect when they are present in anamount of 0.002% or more. An excess amount more than 0.05% aggravatestoughness rather than enhancing the effect. Therefore, the content of Nband Zr should be 0.002-0.05% each.

[0052] V, as well as Nb and Zr, is an element which increases thestrength of steel. An amount of 0.01% or more is necessary for it toproduce its effect. An excess amount more than 0.10% aggravatestoughness rather than enhancing the effect. Therefore, the content of Vshould be 0.01-0.10% each.

[0053] Mention is made below of the manufacturing method according tothe present invention. The method of the invention is characterized inadding Ti in a large amount so that the steel exhibits good corrosionresistance when it is given coating. Unfortunately, Ti precipitates inthe form of TiC, thereby greatly aggravating the toughness of the basemetal. In the production of steel plates, it is important to suppressthe deterioration of toughness due to TiC. There are two ways to achievethis object, (1) by preventing Ti from forming solid solution when steelis heated for hot rolling and quenching, or (2) by making dissolved Ti(in solid solution) harmless. The process of production was investigatedin two ways according to the Ti/C ratio which is either greater than 4or smaller than 4.

[0054] Incidentally, it is not necessary to investigate thedeterioration of toughness due to TiC particles which have precipitatedbefore heating for hot rolling or quenching, because the TiC particlesare too large to affect toughness. In other words, those TiC particleswhich exist before heating for hot rolling are formed during air coolingafter casting, and those TiC particles which exist before heating forquenching are formed during air cooling after hot rolling. Air coolingafter casting is very slow because the slab is thick and hence theprecipitated TiC particles grow and become large. In the case of hotrolling which ends at a high temperature and is followed by air cooling,TiC particles grow and become large, Such grown TiC particles do notaffect toughness and hence they can be neglected.

[0055] Case 1 in which the Ti/C ratio is 4 or less and steel does notundergo quenching and tempering.

[0056] The effect of heating temperature was investigated to find thecondition under which Ti does not form solid solution. Several steelsamples were prepared, with the Ti/C ratio varied for the basecomposition of 0.05%C-0.55%Cu-0.50% Ni-0.05% Ti. In order to makedissolved Ti harmless, hot rolling was carried out in such a way thatthe finish rolling temperature (FRT) is 760° C. (which is close to Ar₃),with the heating temperature varied. Hot rolling, followed by aircooling, gave 25-mm thick steel plates. These steel plates were testedfor toughness. The results are shown in FIG. 1. (The object of makingdissolved Ti harmless is achieved if hot rolling is carried out to suchan extent the low region of the temperature of γ solid solution isreached. Hot rolling at high temperature induces strain to precipitateTiC particles, which become coarser during subsequent rolling to such anextent that they do not match the matrix any longer. Thus it is possibleto suppress the deterioration of toughness.)

[0057]FIG. 1 is a graph showing how toughness varies depending on theheating temperature and the Ti/C ratio. It is apparent from FIG. 1 thatif the heating temperature (T) is (1200−50×Ti/C) ° C. or more (in theregion under the oblique line), the desired value of vE₀>100J isachieved. The lower limit of heating temperature is 850° C. in view ofthe productivity at the time of rolling, because steel is difficult toroll due to increased deformation resistance when the heatingtemperature is low.

[0058] Investigations were carried out into the finish rollingtemperature which is adequate to make the dissolved Ti harmless. Severalsteel samples were prepared, with the Ti/C ratio varied for the basecomposition of 0.05% C-0.55% Cu-0.05% Ti. According to the presentinvention, the steel plate for coating is positively incorporated withNi for improvement in toughness. To see the effect of Ni on toughness,two samples were tested, one containing 0.5% Ni and the other containing1.0% Ni. Judging from the results mentioned above, the heatingtemperature was kept low at 1050° C., which is the lower limit availablefor the continuous heating furnace. Several kinds of 25-mm thick steelplates were prepared by hot rolling, followed by air cooling, with thefinish rolling temperature varied. These samples were tested fortoughness. The results are shown in FIGS. 2 and 3.

[0059] FIGS. 2 and 3 show how toughness is affected by the differencebetween FRT and Ar₃ and the Ti/C ratio, with the amount of Ni kept at1.0% or 0.5%. It is apparent from FIGS. 2 and 3 that if FRT is(Ar₃+50×Ti/C+100×[Ni]²) ° C. or lower (in the region under the obliqueline), the desired value of vE₀≧100J is achieved. For high toughness,FRT should preferably be 700-800° C.

[0060] Case 2 in which the Ti/C ratio is 4 or less and steel undergoquenching and tempering.

[0061] The effect of quenching and tempering temperature wasinvestigated to find the condition under which Ti does not form solidsolution. Several steel samples were prepared, with the Ti/C ratiovaried for the base composition of 0.05% C-0.55% Cu-0.50% Ni-0.05% Ti.This steel was incorporated with 10 ppm of B. As in the case mentionedabove, the amount of Ni was kept at 0.5% and 1.0%. Hot rolling wascarried out such that the heating temperature is 1100° C. (which isgenerally applied to steels for welded structures) and the finishrolling temperature (FRT) is 850° C. Hot rolling, followed by aircooling, gave 25-mm thick steel plates.

[0062] The thus obtained steel plates underwent quenching at variedtemperatures and tempering at 640° C. (which is applied to ordinarysteels (570 N/mm²) for welded structures). Quenching was carried out ata cooling rate of 20° C./s. The resulting samples were tested fortoughness. The results are shown n FIGS. 4 and 5.

[0063]FIGS. 4 and 5 show how toughness is affected by the differencebetween annealing temperature and Ac₃ and the Ti/C ratio, with theamount of Ni kept at 1.0% or 0.5%. It is apparent from FIGS. 4 and 5that if the quenching temperature is (Ac₃+50×Ti/C+100×[Ni]²) ° C. orlower (in the region under the oblique line), the desired value ofvE₀≧100J is achieved. For high toughness, the annealing temperatureshould preferably be 850-880° C.

[0064] The above-mentioned explanation of the quenching temperature isapplicable to reheating-hardening. However, it is also applicable todirect quenching if the heating temperature and FRT are the same asthose in the case where the Ti/C ratio is higher than 4, and the desiredvalue of vE₀≧100J is achieved as a matter of course. Hot rolling isfollowed by water cooling at a controlled cooling rate in view of theplate thickness in order to obtain the desired strength. In the casewhere high toughness is required, FRT should be 700-800° C. and hotrolling should be followed directly by quenching.

[0065] Case 3 in which the Ti/C ratio is higher than 4.

[0066] In the case where the Ti/C ratio is higher than 4, TiCprecipitates incoherently in austenite (without deterioratingtoughness), with very little coherent precipitation (which deterioratestoughness) in ferrite. Therefore, it is basically unnecessary to specifythe heating temperature, FRT, and quenching temperature. In the presentinvention, they are specified as follows in consideration of productioncost and productivity. Heating temperature: 1200° C. as the upper limit(in consideration of fuel consumption) and 850° C. as the lower limit(in consideration of rolling productivity).

[0067] Finish rolling temperature (FRT): 950° C. as the upper limit (inconsideration of strength). Improved strength needs fine crystalparticles. For high toughness, FRT should preferably be 700-800° C.

[0068] Quenching temperature: 950° C. as the upper limit (inconsideration of fuel consumption), and Ac₃ as the lower limit (inconsideration of strength). Hot rolling may be followed directly byquenching. However, there may be an instance where it is necessary tocarry out quenching in the two-phase region in order to achieve a lowyield ratio.

EXAMPLE 1

[0069] The invention will be described with reference to the followingexamples.

[0070] Steel sheets were prepared, each having the chemical compositionas shown in Table 1. They were painted with resin paints as shown inTable 2. The painted film on the steel plate was given a cross cut asshown in FIG. 6. The samples with a cross cut (artificial coatingdefect) were examined for long-term durability by means of acceleratedtest and atmospheric exposure test.

[0071] The painted film on the steel sheet was preceded by sand blastingfor surface preparation, and the painting was accomplished by sprayingso that a painted film thickness of 10 μm was attained. In Table 2showing paints, B denotes butyral resin, P denotes polyester resin, Edenotes epoxy resin, U denotes urethane resin, and F denotes fluorineresin.

[0072] The accelerated test consists of three steps of (1) irradiationwith a carbon arc lamp, (2) dipping in salt water (0.1%, 0.5%, and3.0%), and (3) keeping at constant temperature and constant humidity,which are turned sequentially 60 cycles.

[0073] After the accelerated test, the samples were examined forexternal appearance and corrosion spreading from the cross cut in thepainted film.

[0074] The atmospheric exposure test consists of exposing the samples(directed southward and inclined 30° to the horizontal) to theatmosphere for one year. After the atmospheric exposure test, thesamples were examined for external appearance and corrosion spreadingfrom the crosscut in the painted film.

[0075] Corrosion was rated by measuring the width of corrosion spread ateight points and expressed in terms of average.

[0076] The appearance was rated on a scale of one to ten, with oneindicating the severest damage (or corrosion on the entire surface) andten indicating the best appearance. The relative overall judgment isindicated by ⊚, ◯,

, and X. The results are shown in Table 2.

[0077] It is apparent from Table 2 that the painted steel platesaccording to the present invention are by far superior to thecomparative steel plates, Comparative Examples 1 to 3 are explainedbelow.

[0078] No. 1 represents plain steel. No. 2 represents so-calledcorrosion-resistant steel. Since it contains Cr. it has widely spreadcorrosion due to a lowered pH. No. 3 represents a steel which does notcontain any element (functioning like Cr) which promotes the formationof stable rust and moderate the decrease in pH. Hence it is poor incorrosion resistance. The results shown in Table 2 prove the usefulnessof the present invention. TABLE 1 Chemical composition (mass %) Steel CSi Mn P S Cu Ni Cr Ti Al Ca Others Cu + Ni P_(CM) Ti/C Remarks 1 0.090.21 1.15 0.010 0.003 0.01 0.01 0.03 — 0.026 — — 0.02 0.16 — Comparative2 0.12 0.20 0.75 0.015 0.003 0.36 0.21 0.50 — 0.024 — — 0.57 0.21 —Comparative 3 0.11 0.22 0.66 0.021 0.004 0.34 0.23 0.02 — 0.023 — — 0.570.17 — Comparative 4 0.11 0.22 0.66 0.021 0.024 3.50 0.80 0.01 0.0800.024 — — 4.30 0.34 0.7 Comparative 5 0.15 0.25 1.40 0.010 0.007 0.350.22 0.02 0.050 0.030 — — 0.57 0.25 0.3 Comparative 6 0.05 0.35 1.460.007 0.002 0.54 0.31 0.03 0.030 — — — 0.85 0.17 0.6 Example 7 0.04 0.351.46 0.007 0.002 0.54 0.31 0.03 0.070 — — — 0.85 0.16 1.8 Example 8 0.020.35 1.65 0.010 0.007 0.55 0.30 0.03 0.110 — — — 0.85 0.15 5.5 Example 90.01 0.20 0.52 0.010 0.007 2.23 2.50 0.03 0.050 — — — 4.73 0.21 5.0Example 10 0.01 0.25 1.60 0.010 0.007 0.35 5.53 0.03 0.051 — — — 5.880.22 5.1 Example 11 0.02 0.35 1.65 0.010 0.007 0.55 0.30 0.03 0.0702.05  — — 0.85 0.15 3.5 Example 12 0.05 0.25 1.45 0.010 0.007 0.35 0.200.03 0.050 0.082 0.0035 La:0.004 0.55 0.15 1.0 Example 13 0.05 0.25 1.450.010 0.007 0.40 0.20 0.03 0.080 — 0.0015 Ce:0.0050 0.60 0.16 1.6Example 14 0.05 0.35 1.23 0.007 0.002 0.55 0.30 0.03 0.045 — — B:0.00070.85 0.16 0.9 Example 15 0.06 0.25 1.70 0.010 0.007 0.45 0.20 0.03 0.080— — B:0.0025 0.65 0.19 1.3 Example 16 0.05 0.25 1.51 0.010 0.007 0.510.20 0.03 0.050 — — B:0.0016 0.71 0.17 1.0 Example Nb:0.012 17 0.08 0.251.45 0.010 0.007 0.55 0.20 0.03 0.050 — — V:0.053 0.75 0.20 0.6 ExampleMo:0.20 18 0.11 0.25 1.45 0.010 0.007 0.35 0.22 0.03 0.050 — 0.0025B:0.0008 0.57 0.22 0.5 Example Mo:0.012 19 0.05 0.25 1.45 0.010 0.0070.50 0.20 0.03 0.050 0.105 0.0035 Nb:0.03 0.70 0.16 1.0 Example V:0.035Zr:0.013

[0079] TABLE 2 Accelerated test Accelerated test Accelerated testAtmospheric (0.1% salt water) (0.5% salt water) (3.0% salt water)exposure test Appear- Corrosion Appear- Corrosion Appear- CorrosionAppear- Corrosion Over- ance spread Rat- ance spread Rat- ance spreadRat- ance spread Rat- all Steel Paint (RN) (mm) ing (RN) (mm) ing (RN)(mm) ing (RN) (mm) ing rating Remarks  1 B 3 1.48 X 6 0.53 X XComparative  2 B 4 1.64 X 7 0.44 X X Comparative  3 B 2 2.02 X 7 0.52 XX Comparative  4 B — — — — — — — — X Comparative  5 B 10 <0.50 ⊚ 8 0.70∘ 7 0.67 Δ 9 0.24 ⊚ ∘ Comparative  6 B 9 <0.51 ⊚ 7 0.84 Δ 9 0.26 ∘ ∘Example  7-1 B 10 <0.50 ⊚ 10 0.61 ⊚ 9 0.55 ⊚ 10 0.23 ⊚ ⊚ Example  7-2 P10 <0.50 ⊚ 8 0.66 ∘ 9 0.22 ⊚ ⊚ Example  7-3 E 10 <0.50 ⊚ 8 0.68 ∘ 9 0.23⊚ ⊚ Example  7-4 U 10 <0.50 ⊚ 8 0.64 ∘ 9 0.20 ⊚ ⊚ Example  7-5 F 10<0.50 ⊚ 8 0.66 ∘ 9 0.21 ⊚ ⊚ Example  8 B 10 <0.50 ⊚ 10 0.61 ⊚ 9 0.55 ⊚10 0.23 ⊚ ⊚ Example  9 B 10 <0.50 ⊚ 10 0.51 ⊚ 10 0.18 ⊚ ⊚ Example 10 B10 <0.50 ⊚ 10 0.50 ⊚ 10 0.18 ⊚ ⊚ Example 11 B 10 <0.50 ⊚ 8 0.64 ∘ 8 0.60Δ 9 0.20 ∘ ∘ Example 12 B 10 <0.50 ⊚ 8 0.68 ∘ 7 0.62 Δ 10 0.21 ∘ ∘Example 13 B 10 <0.50 ⊚ 10 0.53 ⊚ 10 0.54 ⊚ 10 0.19 ⊚ ⊚ Example 14 B 10<0.50 ⊚ 10 0.60 ⊚ 9 0.55 ⊚ 10 0.20 ⊚ ⊚ Example 15 B 10 <0.50 ⊚ 10 0.62 ⊚9 0.56 ⊚ 10 0.21 ⊚ ⊚ Example 16 B 10 <0.50 ⊚ 10 0.62 ⊚ 8 0.60 ∘ 10 0.24⊚ ⊚ Example 17 B 10 <0.50 ⊚ 10 0.62 ⊚ 8 0.60 ∘ 10 0.24 ⊚ ⊚ Example 18 B11 <0.51 ⊚ 10 0.64 ⊚ 9 0.55 ∘ 10 0.20 ⊚ ⊚ Example 19 B 12 <0.52 ⊚ 100.56 ⊚ 10 0.50 ⊚ 10 0.16 ⊚ ⊚ Example

EXAMPLE 2

[0080] Steel billets were prepared, each having the chemical compositionas shown in Table 1. They were made into steel plates (25-80 mm thick)under the conditions shown in Table 3. The resulting steel plates weretested for tensile strength, low-temperature toughness, preheatingtemperature to prevent weld crack (according to JIS Z-3158), andtoughness of the heat affected zone. The results are shown in Table 3.For the last item mentioned above, a weld joint was made by electro-gasarc welding (with heat input of 120 kJ/cm). Toughness was measured atthree points: one at the bond (boundary between the welded metal and thebase metal), one 1 mm from the bond toward the base metal, and one 3 mmfrom the bond toward the base metal. The lowest value of threemeasurements was accepted.

[0081] Sample No. 5 (as comparative example) has a high value of P_(CM)and hence has a preheating temperature to prevent weld cracking which isas high as 100° C. In addition, it has a low value of toughness (20 J)at the part affected by welding heat.

[0082] Sample No. 7-6 (as comparative example) has a heating temperaturewhich is higher than that specified in the present invention, Sample No.7-7 (as comparative example) has a finish rolling temperature which ishigher than that specified in the present invention. Therefore, they donot meet the requirement that the base metal should have a value oftoughness greater than 100 J (their values are 60 J and 80 J,respectively). Samples Nos. 8-1 ad 8-2 (as comparative examples) havethe Ti/C ratio exceeding 4. The former has a heating temperature whichis higher than that specified in the present invention. The latter has afinish rolling temperature which is higher than that specified in thepresent invention. Therefore, they do not meet the requirement that thebase metal should have a value of toughness greater than 100 J (theirvalues are 85 J and 76 J, respectively).

[0083] Sample No. 15-1 (as comparative example) has the Ti/C ratioexceeding 4. It has a quenching temperature which is higher than thatspecified in the present invention. Therefore, its base metal has avalue of toughness lower than 80 J.

[0084] Examples according to the present invention are superior in basemetal characteristics, preheating temperature to prevent weld crack, andtoughness of the heat affected zone, regardless of whether the Ti/Cratio is higher than 4 or lower than 4, as shown in Table 2.

[0085] Samples Nos. 15-2 and 19 (as examples) were obtained by hotrolling which was followed by direct quenching. They gave the sameresults as obtained in the case where reheating quenching was carriedout according to the present invention, TABLE 3 Hardening Plate Ar₃ + 50× Ac₃ + 50 × Heating Finish rolling temperature Annealing thickness 1200− 50 × Ti/C + 100 × Ti/C + 100 × temperature temperature Cooling (° C.)(DQ: temperature Steel Ti/C (mm) Ti/C (° C.) Ni² (° C.) Ni² (° C.) (°C.) (° C.) method direct quenching) (° C.)  5 0.3 25 1185 758 853 1100800 Air cooling  6 0.6 25 1170 795 893 1050 780 Air cooling  7 1.8 251110 858 955 1050 780 Water cooling  7-6 1.8 25 1110 858 955 1200 800Water cooling  7-7 1.6 25 1110 858 955 1050 1000 Water cooling  7-8 1.850 1110 858 955 1050 780 Water cooling  8 5.5 25 — Ar₃:750 Ac₃:855 1100900 Water cooling  8-1 5.5 25 — Ar₃:750 Ac₃:855 1250 910 Water cooling 8-2 5.5 25 — Ar₃:750 Ac₃:855 1100 1000  Water cooling  9 5.0 25 —Ar₃:689 Ac₃:841 1100 900 Air cooling 10 5.1 25 — Ar₃:473 Ac₃:735 1100880 Air cooling 11 3.5 25 1025 934 1039  1000 880 Water cooling 12 1.025 1150 820 908 1100 800 Water cooling 13 1.6 25 1120 849 938 1100 820Water cooling 14 0.9 25 1155 828 861 1050 780 Air cooling 15 1.3 25 1135811 913 1050 760 Air cooling 880 640 15-1 1.3 25 1135 811 913 1050 760Air cooling 930 640 15-2 1.3 80 1135 811 913 1050 760 Water cooling DQ640 16 1.0 25 1150 813 907 1050 760 Air cooling 880 640 17 0.6 25 1170789 866 1050 760 Air cooling 870 640 18 0.5 25 1175 776 870 1050 760 Aircooling 860 640 19 1.0 50 1150 817 910 950 760 Water cooling DQ 640 Basemetal characteristics Yield Yield Preheating temperature to CharpyV-notch strength strength protect weld crack (° C.) impact Steel (N/mm²⁾(N/mm²⁾ VE₀(J) (RT: room temperature) properties vEo(J) Remarks  5 453555 100  20 Comparative  6 435 510 >300 <RT 110 Example  7 476 573 >300<RT 100 Example  7-6 460 585 60 <RT Comparative  7-7 453 603 80 <RTComparative  7-8 456 563 >300 <RT 110 Example  8 335 466 >300 <RT 110Example  8-1 355 480 85 <RT Comparative  8-2 363 503 76 <RT Comparative 9 430 520 >300 <RT 110 Example 10 435 534 >300 <RT 115 Example 11 441598 >300 <RT 110 Example 12 445 536 >300 <RT 120 Example 13 437 533 >300<RT 120 Example 14 450 515 >300 <RT 185 Example 15 556 628 >300 <RT 170Example 15-1 568 645 80 <RT Comparative 15-2 528 625 >300 <RT 150Example 16 560 633 >300 <RT 150 Example 17 550 628 >300 <RT 115 Example18 563 635 >300 <RT 155 Example 19 551 635 >300 <RT 120 Example

What is claimed i,s:
 1. A steel plate for paint use which contains C(0.12% or less, excluding O;), Si (1.0% or less, excluding 0%), Mn (2.5%or less, excluding O%), P (0.05% or less, excluding 0%), S (0.02% orless, excluding 0%), Cr (0.05% or less, excluding 0%), Cu (0.05-3.0%),Ni (0.05-6.0%), Ti (0.025-0.15%), Cu+Ni (0.50% or more), and P_(CM)(0.23% or less), in terms of mass %.
 2. A steel plate for paint use asdefined in claim 1, which further contains at least one additionalcomponent selected from Al (0.05-0,50%), Ca (0.0001-0.05%), Ce(0.0001-0.05%), and La (0.0001-0.05%), in terms of mass %.
 3. A steelplate for paint use as defined in claim 1, which further contains B(0.0005-0.0030%), in terms of mass %.
 4. A steel plate for paint use asdefined in claim 2, which further contains B (0.0005-0.0030%), in termsof mass %.
 5. A steel plate for paint use as defined in claim 1, whichfurther contains at least one additional component selected from Nb(0.002-0.05%), V (0.01-0.10%), Zr (0.002-0.05%), and Mo (0.05-0.5%), interms of mass %.
 6. A steel plate for paint use as defined in claim 2,which further contains at least one additional component selected fromNb (9.002-0.05%), V (0.01-0.10%), Zr (0.002-0.05%), and Mo (0.05-0.5%),in terms of mass %.
 7. A steel plate for paint use as defined in claim3, which further contains at least one additional component selectedfrom Nb (0.002-0.05%), V (0.01-0.10%), Zr (0.002-0.05%), and Mo(0.05-0.5%), in terms of mass %.
 8. A steel plate for paint use asdefined in claim 4, which further contains at least one additionalcomponent selected from Nb (0.002-0.05%), V (0.01-0.10%), Zr(0.002-0.05%), and Mo (0.05-0.5%), in terms of mass %.
 9. Amanufacturing method of a steel plate for paint use, said processcomprising hot-rolling a steel plate which is defined in any of claims 1to 8 and contains Ti and C in such an amount that the Ti/C ratio exceeds4, in such a way that the heating temperature is 850-1200° C. and thetemperature at the end of rolling is 950° C. or lower, said hot rollingbeing followed by air cooling or water cooling (at a cooling rate 1°C./s or higher).
 10. A manufacturing method of a steel plate for paintuse, said process comprising hot-rolling a steel plate which is definedin any of claims 1 to 8 and contains Ti and C in such an amount that theTi/C ratio exceeds 4, in such a way that the heating temperature is850-1200° C. and the temperature at the end of rolling is 950° C. orlower, said hot rolling being followed by direct quenching from atemperature of Ar₃˜950° C. or reheating-quenching from a temperature ofAc₃˜950° C., and tempering.
 11. A manufacturing method of a steel platefor paint use, said process comprising hot-rolling a steel plate whichis defined in any of claims 1 to 8 and contains Ti and C in such anamount that the Ti/C ratio is 4 or less, in such a way that the heatingtemperature is 850˜(1200−50×Ti/C) ° C. and the temperature at the end ofrolling is (Ar₃+50×Ti/C+100×[Ni]²) ° C. or lower, which is followed byair cooling or water cooling (at a cooling rate 1° C./s or higher).(where [Ni] represents the content of Ni.)
 12. A manufacturing method ofa steel plate for paint use, said process comprising hot-rolling a steelplate which is defined in any of claims 1 to 8 and contains Ti and C insuch an amount that the Ti/C ratio is 4 or less, in such a way that theheating temperature is 850˜(1200−50×Ti/C) ° C. and the temperature atthe end of rolling is (Ar₃+50×Ti/C+100×[Ni]²) ° C. or lower, which isfollowed by direct quenching from a temperature at the end of rolling orreheating-quenching from a temperature of (Ac₃+50×Ti/C+100×[Ni]²) ° C.or lower, and tempering. (where [Ni] represents the content of Ni.)